臺灣博碩士論文加值系統

防曬乳液中的成分同時包含物理性防曬劑和化學性防曬劑，化學吸收劑para-aminobenzoic acid(PABA)光反應過程會產生不穩定的中間產物，而二氧化鈦和氧化鋅為好的光觸媒，會加速PABA光降解反應，減少PABA之光穩定性。因此藉由脫層蒙脫石的特殊結構以及對PABA的吸附性，改善防曬乳液對皮膚可能的傷害。
本研究利用UV/vis觀察到二氧化鈦、氧化鋅在紫外光區會使PABA之光吸收度上升，脫層蒙脫石(exMMT)則使PABA的304nm的光吸收度下降，而這四種成分皆會加速PABA的光裂解，並以二氧化鈦有較好的催化能力。以PL分析脫層蒙脫石(exMMT)、不同表面性質之二氧化鈦(TTO、TiO2 Rod)和氧化鋅(ZnO)與PABA相互作用後之發光光譜，結果顯示exMMT、TTO和TiO2 Rod使PABA之347nm發光強度提升，除此之外，PABA被TTO和TiO2 Rod吸附後，使PL光譜有紅位移現象，而ZnO能被PABA放射光347nm激發而產生另一個386nm發光波峰。當提高防曬乳液成分之濃度，PL圖譜中之發光強度有整體降低的趨勢。
將製備之防曬乳液塗抹於豬皮上，以ATR-FTIR分析塗抹防曬乳的豬皮於紫外光照射後的組織變化，其結果顯示豬皮本身在紫外線照射下脂質中CO-O的C=O之特徵峰(ν=1745cm-1)、-CH3之特徵峰(ν=1366cm-1)和C-O之特徵峰(ν=1164cm-1)強度有下降之趨勢，並且伴隨脂質過氧化之特峰徵(ν=1260cm-1)強度的提升。來自蛋白質中胺基酸的amide Ⅱ之特徵峰(ν=1539cm-1)、-COO之特徵峰(ν=1574cm-1)以及來自DNA中PO2-非對稱振動之特徵峰(ν=1231)等特徵峰強度會下降，並伴隨胺基特徵峰(ν=3280cm-1)和PO2-對稱振動特徵峰(ν=1095cm-1)強度則是有上升的趨勢。當豬皮塗抹含有PABA、二氧化鈦和氧化鋅的溶液後，經紫外光照射下，由IR圖譜可以觀察到來自蛋白質和DNA之特徵峰的變化與未處理的豬皮類似，而來自脂質經照光而過氧化的特徵峰(ν=1260cm-1)強度有降低之效果，當溶液成分中含有脫層蒙脫石，更是有效阻礙脂質過氧化反應，並隨紫外光照射時間增長，-CO-O的C=O特徵峰強度上升，胺基特徵峰強度下降。

Sunscreen contains both organic and inorganic active ingredients. The organic active ingredient such as para-aminobenzoic acid (PABA) can produce several reactive intermediates under sunlight, and inorganic active ingredients, such as titanium dioxide and zinc oxide, are a well-known semiconductor with photocatalytic properties. When titanium dioxide and zinc oxide are combined with organic filters in sunscreen formulation, they would act as a photocatalyst to accelerate the degradation of organic molecules. To reduce the above-mentioned undesired side effects from UV Sunscreens, we employed the exfoliated montmorillonite(exMMT) as the sunscreen ingredient and investigated its effect on the degradation of organic ingredients and possible protection for the humanskin under UV irradiation.
The experimental results show that the presence of titanium dioxide (TTO and TiO2 Rod) and zinc oxide (ZnO) could increase the UV-vis absorption of PABA at ultraviolet region, but exMMT decreased the UV-vis absorption at 304 nm. All these four ingredients have the catalytic effect on the photochemical reaction of PABA, especially titanium dioxide.
The presence of exMMT and titanium dioxide nanoparticles (TTO and TiO2 Rod) could also increase the PL intensities of PABA at 347nm. Besides, the formation of PABA dimer and aggregation adsorbing on TTO and TiO2 Rod caused a red shift of PL spectrum. Moreover, ZnO could be excited by the emission light from PABA at 347nm and emitted another peak at 386 nm.
To analyze the effect of sunscreen lotion on the changes of pig skin tissue after exposure to UV light, we wiped the sunscreen lotion on pigskin and exposed it to the UV irradiation, which was then subjected to measure the IR spectra by ATR-FTIR. The results showed that for the pristine pigskin, the intensities of characteristic peaks of lipids such as of -C=O at 1745cm-1, -CH3 at 1366cm-1 and C-O at 1164cm-1 decreased with increasing the intensity of 1260cm-1, which has been attributed to the formation of peroxide groups from the peroxidative damage of lipids. The intensities of the characteristic peaks related to the proteins such as amide Ⅱ at 1539cm-1 and -COO non-symmetric stretching vibration at 1574cm-1 decreased with increasing the intensity of 3280cm-1from NH2. As to the characteristic peaks related to DNA, PO2- asymmetric vibration at 1231cm-1 decreased, whereas PO2-symmetric vibration at 1095cm-1 increased. Interestingly, after applying the sunscreen containing the individual PABA, TiO2, ZnO, and their conbinations, the intensity of 1260cm-1 related to the lipid peroxidation weakened, whereas the characteristic peaks of protein and DNA were barely changed compared to the pristine pigskin. When the exMMT was included in the formulation of sunscreen, it significantly hindered the lipid peroxidation along with increasing the intensities of C=O peak and decreasing the intensity of NH2 peak under UV irradiation.

謝誌 .......................................................................................................................................... I
摘要 ............................................................................................................................................... II
Abstract ........................................................................................................................................ IV
目錄 .............................................................................................................................................. VI
表目錄 ........................................................................................................................................... X
圖目錄 .......................................................................................................................................... XI
第一章 緒論 ................................................................................................................................. 1
1-1 前言 ............................................................................................................................... 1
1-2 紫外線 ............................................................................................................................ 3
1-2-1 紫外線的介紹 ........................................................................................................ 3
1-2-2 紫外線的傷害 ........................................................................................................ 4
1-2-3 自由基與反應性氧分子的介紹 ............................................................................ 4
1-2-4 自由基與反應性氧分子對生物體的傷害 ............................................................ 5
1-3 防曬乳液的介紹[8] ....................................................................................................... 7
1-3-1 防曬乳液的成分 .................................................................................................... 7
1-3-2 PABA的介紹 ............................................................................................................ 9
1-3-4 氧化鋅 .................................................................................................................. 17
1-3-5 防曬乳液的潛在問題[8] ..................................................................................... 18
1-4 皮膚的介紹 .................................................................................................................. 20
1-4-1 皮的組織構造 ...................................................................................................... 20
1-4-2 化妝品(包含防曬乳液)的經皮吸收路徑[59] .................................................... 21
1-4-3 皮膚組織研究相關文獻 ...................................................................................... 23
1-5 與本研究相關之項目 .................................................................................................. 28
1-5-1 蛋白質之介紹 ...................................................................................................... 28
1-5-2 皮膚之脂質介紹 .................................................................................................. 31
1-5-3 DNA之介紹 ............................................................................................................ 33
1-5-5 蒙脫石的簡介[77] ............................................................................................... 34
1-6 研究動機 ...................................................................................................................... 40
第二章 實驗設備與方法 ............................................................................................................ 41
2-1 實驗藥品 ...................................................................................................................... 41
2-2 實驗儀器 ...................................................................................................................... 42
2-3 實驗流程 ...................................................................................................................... 43
2-3-1 製備脫層奈米蒙脫石片 ...................................................................................... 43
2-3-2 製備防曬型溶液 .................................................................................................. 44
2-4 測試與分析 .................................................................................................................. 49
2-4-1 X-光粉末繞射分析儀 .............................................................................................. 49
2-4-2 熱重損失分析儀(Thermal Gravimetric Analysis, TGA ) ................................... 49
2-4-3 傅立葉轉換紅外線光譜分析儀(Fourier Transform-Infrared Spectrophotometer, FT-IR) 50
2-4-4 穿透式電子顯微鏡(transmission electron microscopy，TEM) ......................... 50
2-4-5 螢光光譜儀(Photoluminescenece, PL) ................................................................ 51
2-4-6 紫外光/可見光光譜儀(Ultraviolet/ Visible Spectrophotometer) ........................ 51
2-4-7 衰減式全反射之傅立葉轉換紅外線光譜分析(Attenuated-Total-Reflectance Fourier-Transform Infrared Spectroscopy，簡稱ATR-FTIR) ............................................ 52
第三章 結果與討論 .................................................................................................................... 54
3-1 奈米脫層蒙脫石片(exMMT)分析 .............................................................................. 54
3-1-1 熱重損失分析儀之分析 ...................................................................................... 54
3-1-2 穿透式電子顯微鏡之型態分析 .......................................................................... 55
3-2 防曬劑結構與型態分析 .............................................................................................. 57
3-2-1 XRD分析晶型 ........................................................................................................ 59
3-2-2 TEM型態分析 ........................................................................................................ 60
3-3 UV/vis吸收測定無機防曬劑對PABA之影響 ......................................................... 66
3-3-1 exMMT對PABA之UV-vis吸收檢量線的影響 ................................................. 66
3-3-2 TTO對PABA之UV-vis吸收檢量線的影響 ....................................................... 69
3-3-3 TiO2 Rod對PABA之UV-vis吸收檢量線的影響 ............................................... 70
3-3-4 ZnO對PABA之UV-vis吸收檢量線的影響 ....................................................... 72
3-3-5 exMMT對PABA之UV-vis吸收檢量線的影響 ................................................. 72
3-4-1 經照光PABA/exMMT/TTO/PG之UV/vis吸收分析 ...................................... 77
3-4-2 經照光PABA /exMMT/TiO2 Rod之UV/vis吸收分析 .................................... 80
3-4-3 經照光PABA/exMMT/ZnO/PG之UV/vis吸收分析 ...................................... 83
3-5 防曬乳液之螢光光譜儀分析 ...................................................................................... 87
3-5-1 物理性防曬劑對PABA發光光譜的影響 ......................................................... 88
3-5-2 螢光光譜探測PABA之裂解 ............................................................................. 96
3-6 高濃度防曬乳液之分析 ............................................................................................ 115
3-6-1 TEM分析 .............................................................................................................. 115
3-6-2 高濃度防曬乳液之螢光光譜分析 .................................................................... 117
3-7 豬皮之FTIR分析 ..................................................................................................... 134
3-7-1 未經處理豬皮之FTIR分析 ............................................................................. 134
3-7-2 經PABA/PG處理豬皮之FTIR分析 .............................................................. 136
3-7-3 經塗抹TTO/PG溶液豬皮之FTIR分析 ......................................................... 139
3-7-4 經PABA/exMMT/PG處理豬皮之FTIR分析 ................................................ 144
3-7-5 經PABA/exMMT/TTO/PG處理豬皮之FTIR分析 ....................................... 146
第四章 結論 .............................................................................................................................. 150
附錄 ........................................................................................................................................... 159
表目錄
表 1常見防曬乳液的化學性成分[10] ........................................................................................ 7
表 2 Frequencies of vibration bands (cm_1) for DNA isolated from epididymis of low-dose gamma-irradiated ratsa[68]. ................................................................................................. 25
表 3 Frequencies of vibration bands (cm-1) for DNA isolated from epididymis of low-dose gamma-irradiated rats[68] .................................................................................................... 26
表 4 二十種氨基酸之結構 ........................................................................................................ 29
表 5 DNA中的四個鹼基 ........................................................................................................... 33
表 6 低濃度防曬型溶液配方，單位：重量百分比濃度(以Propylene glycol溶劑為100%) ............................................................................................................................................. 46
表 7 高濃度防曬型溶液配方，單位：重量百分比濃度(以Propylene glycol溶劑為100%) ............................................................................................................................................. 47
表 8 使用於豬皮之防曬型溶液濃度配方，單位：重量百分比濃度(以Propylene glycol溶劑為100%) .............................................................................................................................. 48
表 9 TTO之基本性質 ................................................................................................................ 57
表 10 TiO2 Rod之基本性質 ....................................................................................................... 58
表 11 ZnO之基本性質 ............................................................................................................... 58
表 12 IR之波數1260cm-1與1231cm-1之相對強度 ........................................................... 149
圖目錄
圖1- 1太陽光光譜 ....................................................................................................................... 3
圖1- 2 UVC、UVB 及UVA對皮膚的穿透性與傷害之關係[6] ............................................. 4
圖1- 3 Tinosorb M之結構以及對紫外線吸收原理[8] ............................................................... 8
圖1- 4 奈米微粒屏蔽紫外線的原理，其中(a)為反射與(b)為散射方式[8] ............................. 9
圖1- 5 對氨基苯甲酸(Para-aminobenzoic acid，PABA)結構式 ............................................. 10
圖1- 6 不同二氧化鈦的晶型結構 (a)金紅石(b) 銳鈦礦(c) 板鈦礦[22-24] ......................... 12
圖1- 7 二氧化鈦光催化反應機制圖[27] .................................................................................. 13
圖1- 8 4-chlorophenol、azur-B 與α-terpinene之化學結構 .................................................... 17
圖1- 9 氧化鋅的晶體結構[43] .................................................................................................. 17
圖1- 10 Schematic representation of the skin layers and appendages. A. stratum corneum, B. stratum lucidum, C. stratum granulosum, D. stratum spinosum, E. stratum basale, F. papillary layer of the dermis, G. blood vessels, H. duct of sweat gland, I. secretory coil of sweat gland, J. sebaceous gland, K. arrector pili muscle, L. hair bulb, M. hair shaft, N. epidermis, O. dermis, P. hypodermis[58]. ........................................................................... 21
圖1- 11 化妝品成分穿透表皮或細胞間隙經皮吸收路徑 ....................................................... 22
圖1- 12 FTIR images and extracted spectra from a cryo-sectioned pig ear skin sample-with skin surface at the top of the image. Top (from left to right): Integrated intensities of the water OH-stretch region (3650–3000 cm-1), of the amide II band (1590–1480 cm-1), of the CO stretch region (1765–1735 cm-1)and of the CH stretch region (2995–2830 cm-1). (A) Extracted spectra from areas in dermis with high concentrations of proteins/water (black curve) or esters (red curve). (B) Extracted spectrum from an area in epidermis. Circles in the images mark the areas from where the spectra have been extracted. (The colors are visible in the online version of the article.) [63] .................................................................. 24
圖1- 13 The spectra of the normal and cancer tissues at 1800~1500 cm-1 area[69]. .................. 27
圖1- 14 The spectra of the normal and cancer tissues at 1400~1500 cm-1 area[69]. .................. 27
圖1- 15蛋白質的一級結構 ....................................................................................................... 28
圖1- 16 (a)α-helix與(b)β-strand之結構[74] ............................................................................. 30
圖1- 17 肌球蛋白三級結構的飄帶圖，其主要由α螺旋所構成[75] .................................... 30
圖1- 18 角質層脂質Triglyceride(三酸甘油脂)、Ceramides(神經醯胺)、Squalane(鯊烷)及Phospholipid (卵磷脂)之結構 ............................................................................................. 32
圖1- 19去氧核糖核酸(DNA)之化學結構 ................................................................................ 33
圖1- 20蒙脫石的結構[30] ......................................................................................................... 35
圖1- 21 蒙脫石之TEM圖[80] ................................................................................................. 35
圖1- 22 Spatial Arrangement of the Intercalated Ions of (a) L-Phenylalanine in Montmorillonite, (b) L-Tyrosine in Montmorillonite[84] ................................................................................ 37
圖1- 23 (a) siloxane之化學結構(b) 天冬氨酸與蒙脫石吸附之示意圖[85] .......................... 37
圖1- 24 Schematic diagram for the formation mechanism of PMMA and MMT/PMMA nanocomposite latices via soap-free emulsion polymerization[86]. .................................... 39
圖 2- 1 ATR-FTIR模式圖 .......................................................................................................... 53
圖 3- 1 未脫層蒙脫石(MMT)與脫層蒙脫石水溶液(exMMT)之TGA圖 ............................. 55
圖 3- 2 奈米脫層蒙脫石(exMMT)於 (a)倍率30K和(b)倍率50K之TEM圖 .................... 56
圖 3- 3二氧化鈦之XRD圖 ...................................................................................................... 59
圖 3- 4氧化鋅之XRD圖 .......................................................................................................... 60
圖 3- 5 含有TTO之甲醇溶液 於倍率(a) 30K和(b) 100K下觀察之TEM圖，含有PABA與TTO之甲醇溶液於倍率(c) 30K和(d) 100K下觀察之TEM圖，含有PABA、exMMT與TTO之甲醇溶液於倍率(e) 30K和(f) 100K下觀察之TEM圖 ................................. 62
圖 3- 6 PABA被二氧化鈦和蒙脫石吸附之示意圖 ................................................................. 63
圖 3- 7 含有TiO2 Rod之甲醇溶液於倍率(a) 10K和(b) 100K下觀察之TEM圖，含有PABA與TiO2 Rod之甲醇溶液於倍率(c) 10K和(d) 100K下觀察之TEM圖，含有PABA、exMMT與 TiO2 Rod之甲醇溶液於倍率(e) 30K和(f) 100K下觀察之TEM圖........... 64
圖 3- 8含有ZnO之甲醇溶液於倍率(a) 10K和(b) 50K下觀察之TEM圖，含有PABA與 ZnO之甲醇溶液於倍率(c) 10K和(d)50K下觀察之TEM圖，含有PABA、exMMT與ZnO之甲醇溶液於倍率(e) 10K和(f) 50K下觀察之TEM圖 ......................................... 65
圖 3- 9 (a)含有不同濃度PABA之PG溶液與(b) 經normalized處理之UV/vis吸收光譜圖 ............................................................................................................................................. 67
圖 3- 10 PABA在PG溶液中之UV/vis吸收隨濃度改變之檢量線 ...................................... 68
圖 3- 11不同濃度的PABA在含有0.5wt% exMMT的PG溶液中之UV/vis吸收光譜圖 . 68
圖 3- 12 PABA在含有0.5wt% exMMT之PG溶液中之UV/vis吸收檢量線 ...................... 69
圖 3- 13 不同濃度PABA在含有0.5wt% TTO之PG溶液之UV/vis吸收光譜圖.............. 70
圖 3- 14 PABA在含有0.5wt%TTO之PG溶液中的UV/vis吸收檢量線 ............................ 70
圖 3- 15 不同濃度PABA在含有0.5wt% TiO2 Rod之PG溶液中的UV/vis吸收光譜圖 .. 71
圖 3- 16 PABA在含有0.5wt% TiO2 Rod之PG溶液中的UV/vis吸收檢量線 .................... 72
圖 3- 17 不同濃度PABA在含有0.5wt% ZnO之PG溶液中的UV/vis吸收光譜圖 .......... 73
圖 3- 18 PABA在含有0.5wt% ZnO之PG溶液中的UV/vis吸收檢量線 ............................ 73
圖 3- 19 (a)含0.1wt% PABA之PG溶液在不同時間的紫外光照射下之UV/vis吸收光譜圖，(b) 將UV/vis吸收光譜圖normalized到303nm ............................................................. 75
圖 3- 20 (a)含0.1wt% PABA和0.5wt% exMMT之PG溶液在不同時間的紫外光照射下之UV/vis吸收光譜圖，(b) 將UV/vis吸收光譜圖normalized到303nm ......................... 76
圖 3- 21 0.1wt% PABA/PG和0.1wt% PABA/0.5wt%exMMT/PG溶液在不同時間的紫外光照射下之UV/vis吸收 ........................................................................................................ 77
圖 3- 22 (a)含0.1wt% PABA和0.5wt% TTO之PG溶液在不同時間的紫外光照射下之UV/vis吸收光譜圖，(b) 將UV/vis吸收光譜圖normalized到303nm ......................... 78
圖 3- 23 (a)含0.1wt% PABA、0.5wt% exMMT和0.5wt% TTO之PG溶液在不同時間的紫外光照射下之UV/vis吸收光譜圖，(b) 將UV/vis吸收光譜圖normalized到最大光吸收波長 ................................................................................................................................. 79
圖 3- 24 0.1wt% PABA/PG、0.1wt% PABA/ 0.5wt% TTO/PG和0.1wt% PABA/0.5wt% exMMT/0.5wt% TTO/PG溶液在不同時間的紫外光照射下之UV/vis吸收 .................. 80
圖 3- 25(a)含0.1wt% PABA和0.5wt% TiO2 Rod之PG溶液在不同時間的紫外光照射下之UV/vis吸收光譜圖，(b) 將UV/vis吸收光譜圖normalized到304nm ......................... 81
圖 3- 26 (a)含0.1wt% PABA、0.5wt% exMMT和0.5wt% TiO2 Rod之PG溶液在不同時間的紫外光照射下之UV/vis吸收光譜圖，(b) 將UV/vis吸收光譜圖normalized到304nm ............................................................................................................................................. 82
圖 3- 27 0.1wt% PABA、0.1wt% PABA/0.5wt% TiO2 Rod、0.1wt% PABA/0.5wt% exMMT/ 0.5wt% TiO2 Rod/PG溶液在不同時間的紫外光照射下之UV/vis吸收 ........................ 83
圖 3- 28 (a)含0.1wt% PABA和0.5wt% ZnO之PG溶液在不同時間的紫外光照射下之UV/vis吸收光譜圖，(b) 將UV/vis吸收光譜圖normalized到303nm ......................... 85
圖 3- 29 (a)含0.1wt% PABA、0.5wt% exMMT和0.5wt% ZnO之PG溶液在不同時間的紫外光照射下之UV/vis吸收光譜圖，(b) UV/vis吸收光譜圖normalized到303nm ...... 86
圖 3- 30 0.1wt% PABA/PG、0.1wt% PABA/ 0.5wt% ZnO/PG、0.1wt% PABA/0.5wt% exMMT/0.5wt% ZnO/PG溶液在不同時間紫外光照射之UV/vis吸收 .......................... 87
圖 3- 31 (a)含不同濃度PABA之PG溶液的螢光光譜圖，(b) 將螢光光譜圖normalized到最大放光波長 ...................................................................................................................... 88
圖 3- 32 (a)含0.5wt% exMMT之PG溶液與不同濃度PABA在含有0.5wt% exMMT之PG溶液的螢光光譜圖，(b) 將螢光光譜圖normalized到最大放光波長 ........................... 90
圖 3- 33 (a)含0.5wt% TTO之PG溶液與不同濃度PABA在含有0.5wt% TTO之PG溶液的螢光光譜圖，(b) 將螢光光譜圖normalized到最大放光波長 ....................................... 93
圖 3- 34 (a)含0.5wt% TiO2 Rod之PG溶液與不同濃度PABA在含有0.5wt% TiO2 Rod之PG溶液的螢光光譜圖，(b) 將螢光光譜圖normalized到最大放光波長 ..................... 94
圖 3- 35 (a)含0.5wt% ZnO之PG溶液與不同濃度PABA在含有0.5wt% ZnO之PG溶液的螢光光譜圖，(b) 將螢光光譜圖normalized到最大放光波長 ....................................... 95
圖 3- 36含0.5wt% ZnO之PG溶液於激發光347nm所偵測的螢光光譜圖 ........................ 96
圖 3- 37 (a)含0.1wt% PABA之PG溶液紫外光照射不同時間之螢光光譜圖，(b) 將螢光光譜圖normalized至最大放光波長 ...................................................................................... 99
圖 3- 38 (a)含PABA 0.1wt%和exMMT 0.5%之PG溶液經紫外光照射不同時間以及含0.1wt% PABA之PG溶液未經照光之螢光光譜圖，(b) 將螢光光譜圖normalized至最大放光波長 ........................................................................................................................ 100
圖 3- 39 (a)含0.1wt% PABA之PG溶液與不同濃度TTO在含有0.1wt% PABA之PG溶液之螢光光譜圖，(b) 將螢光光譜圖normalized至最大放光波長 ................................. 101
圖 3- 40 (a)含0.1wt% PABA和0.5wt% TTO之PG溶液經紫外光照射不同時間以及含0.1wt%PABA之PG溶液未經照光之螢光光譜圖， (b)將螢光光譜圖normalized至最大發光波長 ........................................................................................................................ 102
圖 3- 41 (a)含0.1wt% PABA之PG溶液、含0.1wt% PABA和0.5wt% exMMT之PG溶液以及不同濃度TTO在含有0.1wt% PABA與0.5wt% exMMT之PG溶液之螢光光譜圖，(b) 將螢光光譜圖normalized至特定的發光波長 ......................................................... 103
圖 3- 42 (a)含0.1wt% PABA之PG溶液與含0.1wt% PABA和0.5wt% exMMT之PG溶液未經照光，以及含0.1wt% PABA、0.5wt% exMMT和0.5wt% TTO之PG溶液經紫外光照射不同時間之螢光光譜圖， (b) 將螢光光譜圖normalized至特定發光波長 ... 104
圖 3- 43 (a)含0.1wt% PABA之PG溶液與不同濃度TiO2 Rod在含有0.1wt% PABA之PG溶液之螢光光譜圖，(b) 將螢光光譜normalized至最大發光波長 ............................. 106
圖 3- 44含0.1wt% PABA之PG溶液未經照光以及含0.1wt% PABA和0.5% TiO2 Rod之PG溶液經紫外光照射不同時間之螢光光譜圖，(b) 將螢光光譜圖normalized至最大發光波長 ............................................................................................................................... 107
圖 3- 45 (a) 含0.1wt%PABA之PG溶液、含0.1wt% PABA和0.5wt% exMMT之PG溶液以及不同濃度TiO2 Rod在含有0.1wt% PABA與0.5wt% exMMT之PG溶液的螢光光譜圖，(b) 將螢光光譜圖normalized至最大發光波長 ................................................. 108
圖 3- 46 (a) 含0.1wt% PABA之PG溶液與含0.1% PABA和0.5wt% exMMT之PG溶液未經照光，以及含有0.1% PABA、0.5wt% exMMT和1wt% TiO2 Rod之PG溶液經紫外光照射不同時間之螢光光譜圖，(b) 將螢光光譜圖normalized至最大發光波長 . 109
圖 3- 47 (a)含0.1wt% PABA之PG溶液以及不同濃度ZnO在0.1wt% PABA之PG溶液之螢光光譜圖，(b)將螢光光譜圖normalize至最大發光波長 ......................................... 111
圖 3- 48 (a)含0.1wt% PABA之PG溶液未經照光以及含0.1wt% PABA和0.5%ZnO之PG溶液經紫外光照射不同時間之螢光光譜圖，(b) 將螢光光譜圖normalized至最大發光波長 ................................................................................................................................... 112
圖 3- 49 (a)含0.1wt% PABA之PG溶液、含0.1wt% PABA和0.5wt%/ exMMT之PG溶液以及不同濃度ZnO在含有0.1wt% PABA與0.5wt%/ exMMT之PG溶液之螢光光譜圖，(b)將螢光光譜normalized至最大發光波長 ................................................................... 113
圖 3- 50 (a)含0.1wt% PABA之PG溶液與含0.1wt% PABA和0.5wt% exMMT之PG溶液未經照光，以及含0.1wt% PABA、0.5wt% exMMT和0.5wt% ZnO之PG溶液經紫外光照射不同時間之螢光光譜圖，(b) 將螢光光譜圖normalized至最大發光波長 ..... 114
圖 3- 51 濃度為2wt%的exMMT之水溶液於倍率(a)30K 與(b)100K之TEM圖 ........... 116
圖 3- 52 含2wt% PABA和2wt% exMMT之水溶液於倍率(a)30K與(b)100K之TEM圖 ........................................................................................................................................... 116
圖 3- 53 含2wt% PABA、2wt% exMMT和2wt% TTO之水溶液於倍率(a)30K與(b)100K之TEM圖 ......................................................................................................................... 116
圖 3- 54 含2wt% PABA、2wt% exMMT和2wt% TiO2 Rod之水溶液於倍率(a)30K與(b)100K之TEM圖 ........................................................................................................... 117
圖 3- 55 含2wt% PABA、2wt% exMMT和2wt% ZnO之水溶液於倍率(a)10K與(b)30K之TEM圖 .............................................................................................................................. 117
圖 3- 56 (a)含2wt% PABA之PG溶液經紫外光線照射不同時間之螢光光譜圖，(b) 將螢光光譜normalized至最大發光波長 .................................................................................... 119
圖 3- 57 (a) 含2wt% PABA之PG溶液未經照光以及含2wt% PABA和2wt% exMMT之PG溶液經紫外光照射不同時間之螢光光譜圖，(b) 將螢光光譜圖normalized至最大發光波長 ............................................................................................................................... 120
圖 3- 58 (a) 不同濃度TTO在含有0.2wt% PABA和之PG溶液之螢光光譜圖，(b) 將螢光光譜normalized至特定發光波長 .................................................................................... 122
圖 3- 59 (a)含有2wt% PABA之PG溶液未經照光以及含2wt% PABA和1.5wt% TTO之PG溶液經紫外光線照射不同時間之螢光光譜圖，(b) 將螢光光譜圖normalized至特定發光波長 ............................................................................................................................... 123
圖 3- 60 含2wt% PABA之PG溶液、含2wt% PABA和2wt% exMMT之PG溶液以及不同濃度TTO在含有2wt% PABA和2wt% exMMT之PG溶液的螢光光譜圖 ........... 124
圖 3- 61 含2wt% PABA之PG溶液與含2wt% PABA和2wt% exMMT之PG溶液未經照光，以及含2wt% PABA、2wt% exMMT和1.5wt% TTO之PG溶液經紫外光照射不同時間之螢光光譜圖 ............................................................................................................ 124
圖 3- 62 (a)含2wt% PABA之PG溶液和不同濃度TiO2 Rod在含有2wt% PABA之PG溶液之螢光光譜圖，(b)將螢光光譜圖normalized至特定發光波長 ................................... 126
圖 3- 63 (a)含2wt% PABA之PG溶液未經照光，以及含有2wt% PABA和1.5wt% TiO2 Rod之PG溶液經紫外光照射不同時間之螢光光譜圖，(b)將螢光光譜圖normalized至特定發光波長 ............................................................................................................................ 127
圖 3- 64 含2wt% PABA之PG溶液、含2wt% PABA 和2wt% exMMT之PG溶液以及不同濃度TiO2 Rod在含有2wt% PABA和2wt% exMMT之PG溶液之螢光光譜圖 .. 128
圖 3- 65 含2wt% PABA之PG溶液、含2wt% PABA和2wt% exMMT之PG溶液未經照光，以及含2wt% PABA、2wt% exMMT和1.5wt%TiO2 Rod之PG溶液經紫外光照射15分鐘之螢光光譜圖 ....................................................................................................... 128
圖 3- 66 (a)含2wt% PABA之PG溶液以及不同濃度ZnO在含有wt% PABA之PG溶液之螢光光譜圖，(b)將螢光光譜圖normalized至最大發光波長 ................................... 130
圖 3- 67 (a)含2wt% PABA之PG溶液未經照光以及含2wt% PABA 和1.5wt% ZnO之PG溶液經紫外線照射不同時間之螢光光譜圖，(b)將螢光光譜圖normalized至最大發光波長 ....................................................................................................................................... 131
圖 3- 68 (a)含2wt% PABA之PG溶液、含2wt% PABA和2wt% exMMT以及不同濃度ZnO在含有2wt% PABA和2wt% exMMT之PG溶液的螢光光譜圖，(b)將螢光光譜圖normalized至最大發光波長 ............................................................................................. 132
圖 3- 69 (a)含2wt%PABA 之PG溶液與含2wt% PABA和2wt% exMMT之PG溶液未經照光，以及含2wt%PABA、2wt% exMMT和1.5wt%ZnO之PG溶液經紫外光照射不同時間之螢光光譜圖，(b)將螢光光譜圖normalized至最大發光波長 ....................... 133
圖 3- 70 未經處理豬皮之FTIR圖譜，(a)以2920cm-1為基準，(b)以1640cm-1為基準，(c)含波數為1231和1260 cm-1之FTIR圖譜 ..................................................................... 136
圖 3- 71 經塗抹PABA/PG溶液的豬皮並以紫外光照射不同時間之FTIR圖譜，(a)以2920cm-1為基準，(b)以1640cm-1為基準，(c)含波數為1231和1260 cm-1之FTIR圖譜 ........................................................................................................................................... 139
圖 3- 72 經塗抹TTO/PG溶液處理的豬皮並以紫外光照射不同時間之FTIR圖譜，(a)以2920cm-1為基準，(b)以1640cm-1為基準，(c)含波數為1231和1260cm-1之FTIR圖譜 ........................................................................................................................................... 142
圖 3- 73 經塗抹PABA/TTO/PG溶液處理的豬皮並以紫外光照射不同時間之FTIR圖譜，(a)以2920cm-1為基準，(b)以1640cm-1為基準，(c)含波數為1231和1260cm-1之FTIR圖譜 ................................................................................................................................... 143
圖 3- 74 經塗抹PABA/exMMT/PG溶液處理的豬皮並以紫外光照射不同時間之FTIR圖譜，(a)以2920cm-1為基準，(b)以1640cm-1為基準，(c)含波數為1231和1260cm-1之FTIR圖譜 ................................................................................................................................... 146
圖 3- 75 經塗抹PABA/exMMT/TTO/PG溶液處理的豬皮並以紫外光照射不同時間之FTIR圖譜，(a)以2920cm-1為基準，(b)以1640cm-1為基準，(c)含波數為1260cm-1之FTIR圖譜 ................................................................................................................................... 149

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